TW493012B - Apparatus for and method of manufacturing plastic container coated with carbon film - Google Patents

Abstract

An apparatus and a method for manufacturing a plastic container coated with carbon film in which the plastic container is accommodated in an external electrode in a state wherein the mouth of the container is abutted on an insulating member, an internal electrode is inserted into the container accommodated in the external electrode, and raw gas is fed into the container in a state of vacuum in the container to generate plasma after high frequency is impressed on the external electrode.

Description

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 493012 A7 B7 V. Description of the Invention (t) [Field of Invention] The present invention relates to a manufacturing device and a manufacturing method for a plastic container coated with a hard carbon film on the inner wall surface. [Background of the Invention] Generally speaking, plastic containers are widely used as packaging containers in various fields such as the food field and the pharmaceutical industry because of their easy-to-form, lightweight, and low-cost characteristics. However, plastic has the property of permeating low-molecular gases such as oxygen and carbon dioxide. In addition, low-molecular organic compounds are adsorbed inside. Compared with other containers such as glass, plastic containers are subject to various restrictions on their use and form I. The term "adsorber" refers to a case where a low-molecular organic compound permeates and diffuses into a plastic composition and is absorbed in the plastic. For example, when carbonated materials such as beer are filled in a plastic container, the contents of the beverage, because they penetrate the inside of the container through plastic, will deteriorate over time, or carbonated gas will be released outside the container through plastic. Make carbonated drinks a discouraged drink. In addition, when a beverage with flavor components such as orange juice is filled in a plastic beverage container, the flavor components (such as limonene in orange juice) of the low-molecular organic compounds contained in the beverage are adsorbed by the plastic, which destroys the balance of flavor components of the beverage , There is no shape of beverage quality deterioration. In addition, the dissolution of low-molecular compounds contained in the composition of the plastic container becomes a problem. That is, when the plastic container is filled with a purity (especially a liquid), the plasticizer and residual monomers contained in the plastic composition, and other additives are dissolved. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). _ 4-(Please read the notes on the back before filling this page)

493012 A7 B7 V. Explanation of the invention (2 Questions and answers to questions. The social nature of pure utensils that can be receivable can be used for internal use and damage. It will be filled, and the filling and filling room will be used as the receiver. After the plastic is filled, the plastic will be used, and the glass will be used in different ways. Net combination washing and washing machine, there is a combination of material and low unit types have halves of odor and mildew, and it is attached when it is sucked. 0 The domestic ring device is self-adhesive and placed in plastic to dissolve. The question is slowly filled with content, and then filled with fresh ingredients, then it is different, and as a low device, it is a plastic material that reduces the volume of the glue. The plastic object is contained in this container because of its distribution. The plastic absorbent is contained in it, but it is still used and the quality is improved. The plastic is used to make the body gas and the container, and it can also be used as a dissection device. The content is not contained in β 0 Rong hib glue is made of machine plastic, and suppressor is a low-end finish. The thinner aluminum or gel plastic under the film is more suitable. The attached layer is used to suck and make it asexual or uniform. The courage is natural, and the solution is to solve the high-grade full-boiled bottle-boiled and cup-boiled 1a. Carbon-coated CB DL 0 vermiculite, rigid.金 出 c (Successful DL technique, thin and thin film η r Γ a (Please read the precautions on the back before filling in this page)

Loading-

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, known as the Hard Weekly High Institute, which is a carbon device that tests the carbon between the carbon and the film. Exact tests such as bottle-burning and cup-burning are performed with sharp technique 〇 i-shaped charcoal ί film quality C fie TL · ® D will be waved, the front surface is first coated with film. The instrument holder Pingkai Teli special edition is described as published in the publication No. Pingkai special Ηϋ Special edition said that the film formed by the package CLD is published in the publication of the paper The paper size is applicable to China National Standard (CNS) A4 specifications (210X 297 mm) 5 repairs | 493012 A7 B7 5. Description of the invention (3) is set as follows. That is, as shown in Fig. 16, a cathode 2 is arranged in a reaction chamber 1 having an introduction port 1A for carbon source gas and an exhaust hole 1B, and an experimental appliance 3 such as a beaker is housed in a recess 2A of the cathode 2. After the grounded anode 4 is inserted inside the experimental device 3, the anode 4 is exhausted from the exhaust hole 1B and the pressure in the reaction chamber 1 is reduced. After the carbon source gas is introduced from the inlet 1A, a high-frequency power source is applied from the high-frequency power source 5 to the cathode 3, and a plasma generated by the carbon source gas is excited to form a DLC film on the surface of the experimental device 3. However, the above-mentioned DLC film forming device accommodates the cathode 2 and the anode 4 in the reaction chamber 1. The volume of the reaction chamber 1 is very large compared with the size of the experimental equipment 3 of the film coating object, and the vacuum operation takes much time. The waste of energy is large. Furthermore, the formation speed of the DLC film formation device is 10 to 1000 Angstroms / minute, and there is a problem that it is difficult to continuously produce the DLC film at a low speed and at low cost. The previous DLC film forming device was intended for experimental devices such as M beakers and flasks. For the purpose of adding added value, the manufacturing cost and manufacturing time are not considered, but the filling containers for beverages such as beer and orange juice. Since a large number of inexpensive products are required, the DLC film forming apparatus cannot be used to manufacture a container for beverages. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). According to the above-mentioned DLC film forming device, the carbon source gas will enter the cathode 2 and the experimental equipment 3 of the coating object. The gap between them cannot be limited to the inner surface of the device 3 and a coating film can be applied. Filling containers for beverages are different from beakers or flasks. There are many opportunities for filled containers to collide or rub against each other during the manufacturing process in the factory or during the sales route. Therefore, when a DLC film is formed on the outside of a filled container for beverages, the | 1UC film is thin and hard, so the DLC film itself will be damaged and the commercial value of the filled container. Therefore, for filling containers for beverages, only the paper size of the container needs to apply the Chinese National Standard (CNS) A4 specification (210X297 mm) ~~ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 493012 A7 B7 V. Description of the invention (4) A DLC film is formed on the inner surface. [Summary of the Invention] The present invention is made to solve the above-mentioned problems. That is, the invention of Θ is to provide a plastic container that can be manufactured while maintaining the characteristics of the plastic container, eliminating the problems of gas barrier properties and adsorption of the plastic, and making it possible to retreat to expand the use form of the plastic container while being cheap. Manufacturing device and manufacturing method of carbon-coated plastic container produced by Dilian Mine and which will not be damaged during use and processing. In order to achieve the above object, the manufacturing device of the carbon film-coated plastic container of the present invention includes a hollow external electrode formed for accommodating a container, and provided with a space similar to the shape of the container outside, and when the container is accommodated When in the space of 3 electrodes, the mouth of the container is blocked while τ insulating the external electrode insulation member, and the internal electrode that is grounded and inserted from the mouth of the container in the space containing the external electrode into the inside of the container , And an exhaust device that communicates with the space of the external electrode and exhausts the gas in the space, and a supply device that supplies the raw material gas to the inside of the space container housed in the external electrode, and a high-frequency power source connected to the external electrode is special mold. Furthermore, the device for manufacturing a plastic container coated with a carbon film according to the present invention has a shape similar to that of the inner wall surface of the container accommodated in the outer electrode space, and the inner electrode is formed with a raw material gas ejection hole. The raw material gas supplied from the supply device is formed by ejecting from the ejection holes of the internal electrode out of a container housed in the space of the external electrode. The ejection holes of the internal electrode are formed in one or more, and are formed in the insulating member. There is a groove, and the mouth of the inner container contained in the external electrode space is blocked by the insulating member. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) "(Please read the precautions on the back before filling this page)

493012 A7 B7 5. In the description of the invention (5), it is characterized by the space formed between the inner wall surface of the external electrode and the outer wall surface of the container, and the inside of the container is connected by a groove portion. In addition, in order to achieve the above object, the manufacturing method of the plastic film-coated plastic container of the present invention is to form a storage container on the external electrode and have a shape similar to the outside of the stored container, and the container stored in the space. The insulating member connected to the mouth insulates the external electrode. While inserting the internal electrode from the mouth of the container inside the container housed in the space, the internal electrode is grounded to K, and the gas in the external electrode space is exhausted to the external electrode housed. After the raw material gas is supplied to the inside of the container in the space, high frequency is applied to the external electrode to make it special mold. The manufacturing device and manufacturing method of the above-mentioned carbon film-coated plastic container are stored by inserting a plastic container into an external electrode. At this time, the internal electrode is inserted into the container. After that, the mouth is blocked by the insulating member and the container is positioned inside the external electrode, and then the inside of the external electrode is closed. At this time, the interval between the inner wall surface of the external electrode and the outer wall surface of the container is maintained substantially uniform, and the interval between the inner wall surface of the container and the outer wall surface of the internal electrode is maintained substantially uniform. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page), and then exhaust the air inside the external electrodes with a venting device to make the inside of the external electrodes vacuum. At this time, not only the air exhausted from the internal space of the container, but also the external space between the external wall surface of the container and the internal wall surface of the external electrode is evacuated by the groove formed in the insulating member to become a vacuum. Thereafter, the raw material gas is supplied from the supply device, and the internal space in a vacuum state is sprayed from a discharge hole formed in the internal electrode. After the source gas is supplied, an external electrode is energized from a high-frequency power source. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). _ 493012 Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, A7, B7. 5. Description of the invention (6) In this energization, between the external electrode and the internal electrode A plasma occurs. At this time, the internal electrode is grounded, but the external electrode is insulated by an insulating member. Therefore, a negative self-bias voltage is generated on the external electrode, and a carbon film is uniformly formed on the inner wall surface of the container along the external electrode. According to the manufacturing device and manufacturing method of the plastic container coated with the carbon film on the upper side, since the manufacturing time can be shortened and energy is not wasted, it is possible to continuously produce inexpensive carbon film coated plastic containers. Further, the carbon film may be formed only on the inner wall surface of the container. The internal electrode is formed into a shape similar to the shape of the inner wall surface, so that a carbon film can be uniformly formed on the inner wall surface of the container. Since the raw material gas ejection holes are formed in the internal electrode, the raw material gas is uniformly ejected from the center portion of the container. Furthermore, the ejection holes are formed in one or a plurality of holes, thereby promoting the diffusion of the raw material gas. Moreover, since the space between the inner wall surface of the external electrode and the outer wall surface of the container is formed in the groove portion of the insulating member, a temperature rise at the time of plasma generation can be suppressed. When the container produced by the present invention is a beverage bottle, it can be used as a recyclable container instead of the previous glass container. In the above-mentioned method for manufacturing a double-glue container coated with carbon film, it is preferable that immediately after the external space between the outer wall surface of the container and the inner wall surface of the external electrode is exhausted, a raw material gas is supplied to the space of the external electrode to be accommodated. As a result, the pressure in the outer space of the container starts to drop slightly later than the pressure in the inner space. The pressure in the outer space immediately after the exhaust is slightly higher than the pressure in the inner space. Therefore, the raw material gas is supplied immediately after the exhaust. That is, the raw material gas sprayed from the inner space will not enter the outer space. This paper size applies the Chinese National Standard (CNS) Α4 size (210X297 mm) (Please read the precautions on the back before filling this page) 11 ϋ-ϋ Β ^ ιϋ mMmmmmtt immTmw il ^ i-m_i- · nm In · — · ϋ · ϋ ϋ — ^ —

W1T 493012 85. A7 B7 V. Description of the invention (7 Body gasification machine with no surface M wall should be inside, the front device M container film can be coated with film, and the carbon borrowed here. The device should be filled with plastic and plastic. Being in the body, leaving the person, etc. Hy H ^ Hr / f 一 可 2 and 1 > 10 time constant gas set the degree of exhaustion ο the air is really close to the short dense air contraction can be in the knee The plastic room is as empty as a membrane pole. The coated electric film is high in carbon and ΓΓ, and it can be lifted to 5 times-the amount of the required amount is Fr tK. The film carbon Mingfa J Benming said that the manufacturing order is not a simple example of the formula gl i, the implementation of the drawing is shown in the figure, and the magnification M is divided into fy 0. The example of the example of the implementation of the picture 't? The face of the plastic film of the plastic film thermal coating compartment example of carbon Shi Mingshi issued this display is not significantly marked as 3 4 _11 film of the same thickness of the film is hard Forming the strip i-the carbon 5 quality picture is shown in hard. Show the figure 5 6 side view picture lir table piece Formed (Please read the notes on the back before filling this page)

The results show that fi--lp is 5 rounds, and the 5th grade is a transparent, oxygen film. The carbon film is hard. The Ministry of Economic Affairs, Central Standards Bureau, Employees Cooperative Co., Ltd. printed purple container plastic film. Hardly made cedar J / Article 5 Figure ο 6 Table TMr: ϊ is 8 Comments can be viewed outside

The film of the II spectrum light Manla is carbonaceous. The thickness of the inner region of the iil15 that passes through the light bar is equal to the thickness of the film. The carbon surface of the hard strips is shaped into the shape of the strips of other pieces of carbon. The 10 quality maps are hard to show, and are not obvious as Λυ ϋ oil. (CNS) Λ4 specification (210X297 male) 1 0.0. Jp ▼ 493012 A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (8) Evaluation result table. Fig. 12 is a table showing evaluation results of oxygen permeability and the like of the hard carbon film formed under the conditions shown in Fig. 10. FIG. 13 is a table showing still other conditions for forming a hard carbon film. Fig. 14 is a table showing evaluation results of the film thickness and the like of the hard carbon film formed under the conditions shown in Fig. 13. Fig. 15 is a table showing evaluation results of oxygen permeability and the like of the hard carbon film formed under the conditions shown in Fig. 13. Fig. 16 is a sectional view showing a prior art. [Detailed Description of the Invention] An embodiment of the present invention will be described below with reference to the drawings. FIG. 1 shows a manufacturing apparatus for manufacturing a plastic container coated with a carbon film of the present invention. In this manufacturing apparatus, a ceramic magnetic insulating plate 11 is mounted on a base 10, and an external electrode 12 is mounted on the insulating plate 11. The external electrode 12 also serves as a vacuum chamber for forming a DLC film, and a space for a container 20 for receiving a coating film object is formed inside the external chamber. The space inside the external electrode 12 is formed slightly larger than the outer shape of the container 20 housed in the space. The container 20 is a bottle for beverages, but other containers may be used. The external electrode 12 is composed of a main body portion 12 A and a cover 12B which is detachably mounted on the upper portion of the main body portion 12A and seals the inside of the main body portion 12A. A high-frequency power source 14 is connected to the external electrode 12 via the integrator 13. Further, the space inside the external electrode 12 is provided with a communication exhaust pipe 15, and the air in the space is exhausted by a vacuum pump (not shown). The internal electrode 16 is inserted into the space of the external electrode 12, and is arranged so as to be located at the center of the space. The internal electrodes 1 to 6 become (Please read the notes on the back first

> .ml atmmtF Βϋϋ Mmmtl eJmMmi ΜΜββ—. HJ— m · ^ I — ^ 装--item and fill out this page)

V1T

This paper size applies to China National Standard (CNS) A4 (210X297 mm) 493012

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (9) The mouth 20A of the container 20 can be inserted into the container and its shape is similar to the internal shape of the container 20. The distance between the external electrode 12 and the internal electrode 16

It is advisable to keep it uniform at any position within the range of 10 to 150 in m. A raw material gas supply pipe 17 is connected to the internal electrode 16. By means of a gas flow controller (not shown), a raw material gas flows into the raw gas supply pipe 17 from an ejection hole 16 A formed in the internal electrode 16. Squirting composition. In order to make the ejected raw material gas uniformly diffuse, it is appropriate to form a plurality of the nozzle holes 16 on the side of the internal electrode 16 as shown in the figure, but if the original gas can be uniformly diffused immediately, the internal § 卩One electrode may be formed on the top of the electrode 16. The internal electrode 16 is grounded via a source gas supply pipe 17. As shown in FIG. 2 and FIG. 3, the insulation plate 11 is enlarged and formed with a plurality of groove portions Η A (four in this embodiment). As can be understood from FIG. 2, the storage container 20 is located on the external electrode 1. 2 Inner container 2 0 mouth 2 0 A is blocked on the insulating plate 1 1, and the outer space 2 1 A of the container and the exhaust pipe 1 are formed between the inner wall surface of the external electrode 12 and the outer wall surface of the container 20 5 is constituted by a trench 11 A. Next, a method for manufacturing a device-shaped salty D L C film by using the upper part will be described as follows. In the external electrode 12, with the lid 12B removed, a plastic container 20 is inserted from the upper opening of the main body portion 12A to be accommodated therein. At this time, the internal electrode 16 is inserted into the container 2 q from the mouth portion 20 A of the container 20. Then, the mouth portion 20 A is blocked on the insulating plate 11. After the container 20 is positioned in the external electrode 12, the carcass 1 2 B is closed to seal the inside of the external electrode 12. At this time, the interval between the inner wall surface of the external electrode 12 and the outer wall surface of the container 20 is kept slightly uniform, and the interval between the inner wall surface of the container 20 and the outer wall surface of the internal electrode 16 is also suitable for this paper. ; fl China National Standard (('NS) Λ4 Specification (210X 297mm) _ ίο _ JtjL. χ (Please read the notes on the back before filling out this page) Order M 493012 Staff Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs Printed A7, B7, V. Description of the invention (1 0) remains slightly uniform. After that, the air inside the external electrode 12 is exhausted by a vacuum pump to make the inside of the external electrode 12 vacuum. At this time, it is formed on the insulating plate 1 1 The groove portion 1 1 A is not only exhausted from the internal space 2 1 B of the container 20 but also exhausted from the external space 2 1 A between the outer wall surface of the container 20 and the inner wall surface of the external electrode 12 to form a vacuum state. This is If the external space 2 1 Λ is not a vacuum, when the plasma to be described later occurs, the external space 2 1 / \ becomes high temperature, which has a negative impact on the plastic material of the container 20. The vacuum at this time The degree is preferably 1 0 — 2 to 1 0 — 5 t 〇rr The reason is that there is too much impurities in the container at the vacuum degree of 10-1 Μ, and when the vacuum degree is less than 10-5, the relationship between excessive time and energy is required for exhaust. After that, the gas flow rate is not shown. The controller bakes the raw material gas to the raw material gas supply tube 17 and supplies the raw material gas of the carbon source from the ejection holes 16 formed in the internal electrode 16 to the internal space 2 1 Β which is in a vacuum state. The raw material gas K 1 to 1 〇 〇m 1 / m ί η is suitable for baking, the internal space 2 1 Β is adjusted due to the supply of the raw material gas pressure within the range of 0.5 ~ 0. 0 1 t 〇rr. External space 2 1 Λ is exhausted by the groove 1 1 A. Therefore, the pressure in the outer space 2 1 A is slightly lower than the pressure in the inner space 2 1 B. Therefore, immediately after the exhaust, the outer space 2 1 Λ The pressure is slightly higher than the internal space 2 1 B. Therefore, the raw material gas is supplied immediately after venting, that is, the raw material gas sprayed out of the internal space 2 1 Β will not enter the external space 2 1 Λ. Use room temperature krypton gas or Liquid aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated carbons Type, nitrogen-containing hydrocarbons, etc. as the raw material gas. Especially (please read the precautions on the back before filling in this page). · 1T wood paper and paper size standard towel valve valve standard winter (CNS) Λ4 specification U10X297 male f)! 3 Amendment printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, 493012 A7 B7 V. Description of the invention (u) Benzene, toluene, 0-xylene, m-xylene, p-xylene with a carbon content of 6K Cyclohexane is suitable. This raw material can be used alone or as a mixture of two or more kinds of gases. Furthermore, these gases may be diluted with a rare gas such as argon or helium for use. After the raw material gas is supplied, the external electrode 12 is energized from the high-frequency power source 14 via the adapter 13. Due to this energization, plasma is generated between the external electrode 12 and the internal electrode 16. At this time, the internal electrode 16 is grounded, but the external electrode 12 is insulated by the insulating plate 11. Therefore, a negative self-bias voltage is generated on the external electrode 12, so that DLC is uniformly formed on the inner wall surface of the container 20 along the external electrode 12. membrane. That is, the formation of the DLC film on the inner wall surface of the container 20 is performed by the mosquito plasma CVD method. According to these young daughter CVD methods, the temperature at the time of DLC film formation can be set to a lower temperature by using low-temperature plasma. Therefore, it is suitable for the processing of poorly heat-resistant articles such as M plastics as substrates, and can be cheaper and cheaper. A larger area of DLC film is formed. The term "low-temperature plasma" refers to a plasma in which the temperature of electrons in the plasma is high while the temperature of the chicks and neutral molecules is significantly lower than the temperature when the reactor is maintained at a low pressure, that is, , In terms of the unbalanced state of the young daughter body. When a plasma is generated between the external electrode 12 and the internal electrode 16, electrons are stored in the inner wall area of the insulated external electrode 12, and the external electrode 12 becomes self-biased to a negative potential. Due to the accumulated electrons, a potential drop of about 500 to 1000 V occurs on the external electrode 12 side. At this time, there is a carbonic acid gas that is a carbon source in the embryo body. Therefore, * Ionization # is positive. The carbon source is selected. This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm). (Read the notes on the back before filling out this page)

493012 Printed by A7 B7, Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the Invention (1 2) It collided with the inner wall surface of the container 2 0 along the external electrode 12. Then, the approaching carbon was combined with each other. The inner wall surface of 0 forms a hard carbon film formed by an extremely fine DLC film. In addition, the so-called hard carbon film formed of a DLC film is also referred to as an i-carbon film or a hydrogenated amorphous carbon film (U-C: II), and M S P 3 is an amorphous carbon film combined as a main body. The thickness of the DLC film is determined by the output of high frequency, the pressure of the raw material gas in the container 20, the supply gas flow rate, the plasma generation time, the self-bias voltage, and the type of the raw material. The absorption inhibition effect and the improvement effect of the gas barrier property, and the adhesiveness with plastic, durability and transparency, etc., are preferably K0.05 ~ 5 / im. In addition, the film quality of the DLC film also depends on the high-frequency output, the pressure of the raw material gas in the container 20, the flow rate of the tritium gas, the plasma generation time, the self-supplying pressure, and the type of raw material. The increase in high-frequency output reduces the pressure of the raw material gas in the container 20, reduces the supply gas flow rate, increases the self-supply bias voltage, and reduces the carbon number of the raw material. All of these have become the hardening of the DLC film, increasing the fineness and compressive stress. Causes of increased and increased vulnerability. Therefore, to maintain the adhesion to plastic and the durability of the film, it is necessary to maximize the absorption suppression effect and gas barrier effect of low molecular organic compounds, that is, set the high frequency output to 50 ~ 100 00 W, the container The pressure of the raw material gas in 2 0 is 0 · 2 0 ～ 0, 0 1 t 〇rr, the flow rate of the supply gas is 1 0 ～ 5 0 m 1 / mi η, and the self-bias voltage is -2 0 0 ~ -1 0 0 0 V, the amount of carbon in the raw material gas is preferably about 1 to 8. Then, in order to improve the adhesion between the DLC film and the plastic, before forming the DLC film, perform plasma treatment with an inorganic gas such as argon or oxygen to make Containers within 20 This paper size applies to Chinese national standards (CN, S) Λ4 specifications (21 × 297 mm) 1 5 correction page (please read the precautions on the back before filling this page) 493012 Central Bureau of Standards, Ministry of Economic Affairs Printed by employee consumer cooperative A7 B7 ____ V. Description of invention (13) Wall activation is also possible. FIG. 4 is a side sectional view showing a plastic container having a DLC film formed by the above-mentioned method. In the figure, 20A is a plastic material, and 20B is a DLC film formed on the inner wall surface of the plastic material 20A. Thus, using the DLC film 20B to coat the inner wall of the plastic container 'not only significantly reduces the permeability of low molecular inorganic inorganic substances such as oxygen and carbon dioxide, but also completely suppresses various low molecular organic compounds with odor. In addition, the original transparency of the plastic container is impaired due to the formation of the DLC film. Furthermore, the plastic materials forming the container 20 are, for example, polypropylene resin, polypropylene resin, polyethylene, cycloolefin copolymer resin, polyethylene terephthalate resin, polyolefin resin, and ethylene-ethylene. Alcohol copolymer resin, poly-4-methylpentane-1 resin, polymethyl methacrylate, acrylonitrile resin, polyvinyl chloride resin, polyvinylidene chloride resin, acrylonitrile styrene resin, acrylonitrile '' Butadiyne · Styrene resin, Polyamide resin, Polyamide resin, Polyacetal resin, Polycarbonate resin, Polybutylene terephthalate, Ion resin, Polysulfone resin * And 4-fluorinated ethylene resin. Regarding the plastic container coated with carbon film produced by the above manufacturing apparatus and manufacturing method, (l) the thickness of the DLC film, (2) the density of the DLC film, (3) the adhesiveness 1, (4) the adhesiveness 2, (5) Alkali resistance, (6) Carbon dioxide gas barrier properties, (7) Oxygen barrier properties, (8) Adsorption properties of low molecular organic compounds (fragrance components) are as follows. In addition, each evaluation method is performed by spinning down. (1) The thickness of the DLC film is masked with universal ink or the like on the inner surface of the container in advance. After covering the DLC, the mask is removed with diethyl ether, etc., and the surface shape measuring device Dickard 3 manufactured by Bucc (VECC0) is used. (DECTACK 3) The film thickness was measured. This paper size applies to China National Standard (CNS) A4 (210X297 mm) 16 (Please read the precautions on the back before filling this page)

Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 493012 A7 _B7__ V. Description of the Invention (14) (2) D L C Film Density Determine the weight difference after film formation, and calculate the density from the film thickness obtained in (1). (3) Adhesiveness 1 According to the J1Sk 5400 square grid tape method, the above conditions are applied to the side wall of the container. 1. The interval between cuts: 1mm 2. The number of square grids: 100 (4) Adhesiveness 2 The continuous weighted scratch tester Heidon 22 (HEID0N 22) manufactured by Xindong Science Co., Ltd. is used for the container under the following conditions The side wall portion is implemented. The degree of close contact is K 1 plus the vertical weight of the scratched needle at the beginning of film peeling. 0 1. The material of the scratched needle, shape, diamond, 50 a R. 2. Weighting speed: 100g / min 3. Bench speed: 1000mm / min (5) Ruggedness resistance Sodium hydroxide is added to make a 10-weight alkaline solution into the container and immersed in hot water at 75 ° C 24 hours, observe the shape change of DLC 'youyou peel. As a result, those who had no change after 24 hours of immersion on M were superior, and those who had no change after 12 hours of immersion on K were good. (6) Carbon dioxide gas barrier properties A PERMATRANC-4 manufactured by MODERN CONTROL was used at 25 ° C1 to measure the carbon dioxide gas permeability. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm). _ 17-(Please read the precautions on the back before filling this page)

-, 1T 493012 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (15) (7) Oxygen-barrier use of OX-DU DU DU YING (MODEL CONTROL) manufactured by MODERN CONTROL (eight m / L · :), the oxygen permeation amount was measured at 40 1C. (8) Low-molecular organic compounds (fragrance ingredients) ϋϋ Use of odor-containing low-molecular organic compounds (fragrance ingredients) as an environmental material, KK-Matsuno et al. (J. Ajic.Food.Chem. 1992, 40, 1902-1905) for reference. The sequence is as follows. 1. Prepare a 0 · 3 sugar ether solution containing 1 0 0 ρ P m of various flavor ingredients (η-octane, η-octanal, η-octanol, ethyl hexanoate, d-limonene), As the test sample fragrance solution. 2. Fill the container with 700 ml of the test sample fragrance solution, cover it, and store it at 20 ° C for one month. 3. After one month, discard the test sample fragrance solution and use 60 ° The inside of the container was washed with distilled water of C and then dried. 4. Fill with diethyl ether and extract the fragrance component absorbed in the container. 5. Remove the diethyl ether from the container and add sodium sulfate anhydride to dehydrate it. 6. Pentylbenzene As an internal standard, quantitative analysis was performed with a gas chromatograph. As a result, when an aqueous solution containing 1 ppm of the fragrance component was present in the container, the fragrance component absorbed in the container was expressed. Therefore, the unit is wg / F > pm / |) 〇ttle [Experiment 1] A 700 ml polyethylene terephthalate resin container (PET resin made by Mitsui PET Resin Co., Ltd., type L125) was used as a plastic container and housed in the external electrode 12 of FIG. 1 and fixed. . This paper size applies to China National Standard (CNS) Α4 (210X 297mm) (Please read the precautions on the back before filling out this page)-, ιτ The consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs DU 493012 A7 B7 V. Description of the invention (1 6) Second, start the vacuum pump, external Inside the electrode 12 becomes 10 _ 4 t 〇rr After the vacuum (back pressure) at K, the flow rate of K 3 0 m 1. Mi ri is introduced into the argon into the plastic container, so that the pressure becomes 0. 4 t 〇rr. For pre-treatment, the inner surface of the R f electric plasma was treated with MW 300 W. After that, argon was used as an auxiliary gas to introduce Φbenzene, cyclohexane, benzene P-xylene, benzene or P- Xylene was used as the raw material gas in the container, and the inner surface of the container was evenly coated with DLC under the conditions shown in Figure 5. [Test results] Film thickness, film formation speed, density, adhesion 1, adhesion 2, alkali resistance The results of each evaluation are shown in Fig. 6. The density is more than 2.0 g / cm3, and the film (the system is very fine. The results of the square lattice test can show the adhesion with the polyethylene terephthalate resin. For good, it can be fully resistant to practical use. Also, alkali resistance is no problem, the film of DLC is extremely It can be understood that the polyethylene terephthalate resin can be completely protected. The results of the oxygen permeability, carbon dioxide permeability, and the degree of absorption of various perfume components are shown in Fig. 7. The delicate DLC film is not only completely inhibited The absorption of fragrance ingredients and effectively inhibits the transmission of carbon dioxide. Also shown in Figure 8 is the transmission spectrum in the ultraviolet visible light field of the trunk of a plastic container coated with SDLC film on the inside. From about 500 nm to about 500 nm In the ultraviolet range, the transmittance decreases sharply, which means that the coating of the DLC film can effectively suppress the degradation of the contents due to ultraviolet rays. Figure 9. Raman spectrum of a film coated on the trunk of a plastic container under the conditions of M test 1. This paper size applies to Chinese National Standards (CNS) Λ4 specifications (210X297 mm) 1 9 Shura ▼ Pack-(Please read the precautions on the back before filling this page) Order Φ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs This paper size applies the Chinese National Standard (CNS) A4 (210X297 mm) 493012 A7 B7 V. Description of the invention (17) [Experiment 2] In addition to using 700 ml of polypropylene ♦ styrene copolymer resin container ( The product of Mitsubishi Monsanto Chemical Co., Ltd .: PAN resin, model L700) is used as the plastic container K, and the rest is the same as that of Test 1 to form a DLC film on the inner surface of the container. The conditions for forming the DLC film are as shown in FIG. 10. In the same manner as in Test 1, tests were performed on film thickness, density, adhesion 1, adhesion 2, alkali resistance, carbon dioxide gas barrier, oxygen barrier, and adsorption of low-molecular organic compounds. [Test results] The results of the tests on film thickness, density, adhesion 1, adhesion 2, and alkali resistance are shown in Fig. 11. Regarding the film thickness and density as shown in Equation 1¾, the situation is good. As for the adhesion 1 and the adhesion 2, if there is no problem in the test 1, the adhesion between the DLC and the polypropylene styrene copolymer resin is the same as that of the polyethylene terephthalate resin, and there is no practical use. problem. Fig. 12 shows the results of the degree of absorption of various perfume components, such as transmittance and carbon dioxide transmittance. That is, the gas barrier properties of polypropylene and styrene copolymer resins are inherently excellent. Furthermore, after coating with DLC, it became clear that the permeation amounts of oxygen and carbon dioxide reached extremely low levels. The absorption amounts of various perfume ingredients are the same as those in Experiment 1, and there is no problem in the sensory evaluation under the detection limit K. [Experiment 3] A DLC film was formed on the inner surface of the container in the same manner as in Experiment 1, except that a container made of a cycloolefin copolymer resin (product of Mitsui Petrochemical Co., Ltd .: COC resin model APL6015) with a capacity of 700 ml was used. Shape -20-(Please read the notes on the back before filling this page)

493012 87. Π · 1 6 V. Description of the invention (is into a thick film 2 ο The properties show the dense 3 Ti, Figure 丨 If the film is tightly connected, the method is to block the acid 1 carbon The test is the same as that of the alkali resistance test. It is a combination of wy S and sexual absorption.) B The machine has a low sub-score and sexual resistance. He, any 2 sex 2 acceptance test, and 1i Ti sex acceptance test are the same, such as degree. Secret, the thickness of the 14 film is round, such as Ruguan is sucked and divided into different kinds of fragrance and DL degree and the device Permeable carbon gelled plastic oxygen is the second one, especially degree. The problem is that the oxygen is not equal to the average II no. Good is the polarity. The denser ene is higher than the ratio is the amount of resin. It is shown in Figure 2 that the carbon 15 is transformed into oxygen. For this reason, the DL causality is overlaid, and the fat longitude tree is painted, but the hydrocarbon system is large, the water is low, and the phase is HU to Ηϋ $. Ming Shuo Zhi Rong Rong Jian Yuan [ο 2 极 电7 \ J- Portuguese

Likou P --------_ (Please read the notes on the back before filling in this page. Printed by the Ordnance Disposal Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

Ti 6 5 4 ri ii 1i ii i _ -1 pieces of structure edge gas ¥ ® ί source plate electric tube edge of the gas outlet frequency frequently 0 inline high spray ditch standing η ditch paper size suitable for Sichuan China National Standard (CNS ) Λ4 specification (210X 297 mm)-21 correction page

Claims (1)

493012 The scope of the patent application is 87 · 11 · 1. The amendment is correct B. It is said that there is a plastic container coated with plastic for coating. It has a carbon type. With the shape of the compartment and the shape of the space in the outer space of the pole part of the shape of the compartment under the M block P, timely, timely, the internal electrode structure of the edge of the absolute electrode Electricity. Lr RH cuts off the outer margin of the capacitor, the outer pole of the capacitor β, the outer pole of the capacitor income: 3 plug section and P, the pole capacitor section from the inside The ground side is connected to the inner space containing the gas hF. The space inside kF 0 is vacated, and the outer pole electrode of the inner space is connected to the inner space of the supply side inner space. Outside of the electrical department, the container contains the plastic film coating for the container. Membrane g electric source frequency of the carbon source lr. High-level siege fan electric power department special, please apply in the application, and then install the device inside the retaining wall to describe the former and the forming system. Inside the Electrode Department οιη The top 14 compartments in the shape of the bottom M The device printed and manufactured by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs · Items made of carbon in plastic-coated plastic coatings 1 × No. Fan Li Zhuan, please click Shen Qiru, 3 units are installed to receive the electric body of the nozzle before spraying out from the hole. The material inside the gas is from the internal element system, and the shape of the gas inside the electrode is between the electrode and the electrode of the electric source. The front part of the electric supply part is placed in the plastic film coating. Item 3 '' A container made by its 4 I device This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 493012 A8 B8 C8 D8 6. The number of applicants for the patent scope is multiple or 1 The Ministry of Internal Affairs and Communications requested that its description be as follows: The first 5 devices made of plastic, coated with plastic, and coated with carbon, are connected to the inner surface of the container and the inner surface of the trench.口 立 口 立 口 fKl fK · -— 一 —μί In the evening, I described it in the container, and when the part is, the part that forms a hollow edge between the grooves must be connected to the surface. The wall of the front part of the mouth is made of plastic and plastic film coated with carbon. Item 1 Fan Lizhuan, please apply for it, 6. Installation is a special method. The container is used for coating plastic film for plastic bottles. The carbon container is described as the first one. The holding surface is ruu. The container is described as the front and the container is formed as the electrode part. The evening is inside the container. The space should be inserted into the mouth of the M-shaped space, and the inner part should be inserted into the mouth. The internal and external electricity received at the electrical port of the pole block is received outside the internal capacity, the rear body air, the original air inside the body air, and the raw air supply side of the body supply power to the pole. The ground is connected to the poles and poles and the power supply department at a high altitude (please read the precautions on the back before filling out this page), 1T printed plastic container film made by the legal department of the Central Standards Bureau Employees Consumer Cooperative of the Ministry of Economic Affairs. Item 7 of the coated carbon, Fan Li special, please string in the container made of plastic film coated carbon ο _ of the person I, item 7Γ Fan Di, the material used for the bottle, please Rong Shenshu As described in the first nine devices, the front part of the pole-shaped part in the forming plane will be described before, and the other part of the inner surface of the holding plane will be described. The following description of the device in the wall holding the dimension surface applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) for the paper size. 1-Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 493012 A8 B8 C8 D8 6. The shape of the interval under the patent application scope M. 10. The method for manufacturing a plastic container coated with a carbon film according to item 7 of the scope of patent application, wherein a groove portion is formed on the front insulation member, and the inner space M of the container and the outer wall surface of the container and external electrodes are formed by the groove portion. The outer space between the inner wall surfaces is also exhausted at the same time. 11. The method for manufacturing a plastic container coated with a carbon film according to item 10 of the scope of patent application, wherein the external space between the outer wall surface of the front container and the inner wall surface of the external electrode is just after the air is exhausted, and the external electrode is accommodated in the external electrode The raw material gas is supplied inside the container in the space. 12. According to the method for manufacturing a plastic container coated with a carbon film according to item 7 of the scope of the patent application, before coating the carbon film on the plastic container, an inorganic gas is used for plasma treatment. 13. The method for manufacturing a plastic container coated with a carbon film according to item 7 of the scope of patent application, wherein the vacuum degree of the exhaust gas in the space of the external electrode is 1 0-2 to 1 0-5 't 〇rr Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)-Order